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Chng IV

Ph cng hng t ht nhn (NMR)


I. C s vt l hc
1. Ht nhn trong t trng
Ph NMR l mt phn ca ph cao tn. Tng tc vi ht nhn c to ra vi sng

radio (108 106Hz).


1.1. Ht nhn trong t trng
Ph NMR nghin cu nhng bc chuyn ca cc mc nng lng ca ht nhn

thun t (ht nhn c t tnh). Cc mc nng lng ny l bng nhau, bi vy cn mt


tng tc gia ht nhn vi mt t trng.
Ht nhn c momen t (magnetic moment) c th c nhng trng thi nng lng

khc nhau khi trong mt t trng.


Bng 1. Nhng ht nhn hay gp trong cc hp cht hu c
ng
v
1

H
D
7
Li
9
Be
10
B
11
B
12
C
13
C
14
N
15
N
16
O
17
O
19
F
23
Na
24
Mg
25
Mg
27
Al
28
Si
29
Si
31
P
32
S
33
S
35
Cl
37
Cl
2

% trong t
nhin

S
proton

99,98
1,56.102
92,57
100
18,83
81.17
98,89
1,108
99,635
0,365
99,96
3,7.10 -2
100
100
89,9
10,05
100
95,3
4,70
100
99,26
0,74
75,4
24,6

1
1
3
4
5
5
6
6
7
7
8
8
9
11
12
12
13
14
14
15
16
16
17
17

S
ntron
1
4
5
5
6
6
7
7
8
8
9
10
12
12
13
14
14
15
16
16
17
18
20

nhy
tng i *

1/2
1
3/2
3/2
3
3/2
0
1/2
1
1/2
0
5/2
1/2
3/2
0
5/2
5/2
0
1/2
1/2
0
3/2
3/2
3/2

2,793
0,857
3,256
1,177
1,801
2,688

1,000
9,64.103
0,294
1,39.102
1,99.102
0,165

Tn s
NMR
(MHz)**
100
15,4
38,8
14,0
10,7
32,2

0,702
0,404
0,283

1,59.102
1,01.103
1,04.103

25,1
7,2
10,1

1,893
2,627
2,216

2,91. 10 -2
0,834
9,27. 10 -2

13,5
94,0
26,5

0,855
3,639

2,68. 10 -2
0,207

6,1
26,0

0,555
1,131

7,85. 10 -2
6,64. 10 -2

19,9
40,5

0,643
0,821
0,683

2,26. 10 -3
4,71. 10 -3
2,72. 10 -3

7,67
9,79
8,15

49

ng
v
39

K
As
79
Br
81
Br
115
Sn
117
Sn
119
Sn
199
Hg
201
Hg
203
Tl
205
Tl
207
Pb
75

% trong t
nhin

S
proton

S
ntron

nhy
tng i *

93,08
100
50,57
49,43
0,35
7,67
8,68
16,86
13,24
29,52
70,48
21,11

19
33
35
35
50
50
50
80
80
81
81
82

20
42
44
46
65
67
69
119
121
122
124
125

3/2
3/2
3/2
3/2
1/2
1/2
1/2
1/2
3/2
1/2
1/2
1/2

0,391
1,435
2,099
2,263
0,913
0,995
1,041
0,499
0,607
1,596
1,611
0,584

5,08. 10 -4
2,51. 10 -2
7,86. 10 -2
9,84. 10 -2
3,50. 10 -2
4,53. 10 -2
5,18. 10 -2
5,72. 10 -3
1,90. 10 -3
0,187
0,192
9,13. 10 -3

Tn s
NMR
(MHz)**
4,67
17,1
25,1
27,0
31,1
37,0
37,6
17,9
7,24
57,0
57,7
20,9

*) Spin v momen t ca ht nhn


Thnh phn ht nhn gm proton v neutron u c xung quay ring (rotation

impuls) ca mnh, k hiu l pk , cn gi l spin.


Ngc vi cc xung quay kinh in (rotation impuls), spin c nhng gi tr ngt

qung.
Spin ht nhn c to thnh v phng din vect l s cng ca thnh phn ht

nhn (proton v neutron) theo cng thc :


(1)

h = hng s Planck
I = s lng t spin ht nhn
i vi cc ng v ht nhn khc nhau I c th bng 0, 1/2, 1, 3/2, ..., 7.
Khi s th t (s proton) v khi lng (s proton + neutron) ca mt ht nhn u

l s chn th I = 0 ht nhn khng c spin. i vi nhng ht nhn c c 2 s l s l


hoc khi lng l s l th I c th l 1/2, 3/2, 5/2 .... Trng hp s th t l, khi lng
chn th I = 1, 2, 3, ...
Spin ht nhn gn vi mt momen t k :

(2)

k = pk

= t l hi chuyn t ca mt ht nhn

50

*) Hin tng tch trng thi nng lng


Khi khng trong mt t trng th cc trng thi nng lng ca mt dipol ht nhn
l bng nhau. Chng cng c mc nng lng Eo.
Trong mt t trng ng nht, khng i, moment ht nhn tng tc vi t

trng. Nu ta cho trc z trng hng vi ng sc t trng Hx = Hy = 0.


Ta c :

p k z = m Ih

(3)

k z = m Ih

(4)

E = h

Eo

mI = s lng t spin t

Hz = 0

Hz

Mi ht nhn s c (2I + 1) v tr momen t trong t trng Hz.


Momen t ca nhng ht nhn c I =

1
, v d : 1H,
2

13

C,

19

F,

31

P,

15

N s c hai

trng thi trong trng Hz l :

mI = +

1
v
2

mI =

1
2

kz

m = +

1
2

kz

m = -

1
2

m = +

1
2

Momen t ca ht nhn c I = 1 s c 3 v tr l :

mI = 1

kz

mI = 0

kz

mI = 1

kz
E

k
k

m = 0
m = -

1
2

Cc trng thi khc nhau trong t trng Hz s c mc nng lng khc nhau.
Nng lng tng tc E gia k vi t trng Hz l :
z

1
1
(5) E = m I hH z trng thi mI = c nng lng cao hn trng thi mI = + .
2
2

51

Khong cch gia hai trng thi nng lng lin nhau l :

E = m I hH z

(6)

E trong NMR t l thun vi cng t trng Hz.

2. Qu trnh cng hng


*) iu kin cng hng
Bc nhy gia hai mc nng lng lin k s xy ra khi ht nhn c mt in t

trng cao tn xoay chiu c tn s cung cp nng lng ph hp vi phng trnh (6).
Trng hp ny s xut hin s cng hng gia trng xoay chiu v ht nhn.
Quy tc cng hng :

mI = 1

iu kin cng hng : E = h = hH z


"Ph NMR ch quan st thy vi iu kin k z 0 v t trng Hz 0. Ht nhn
c I = 0, k = 0 s khng c ph NMR.
*) S chim ch trong cc mc nng lng.
Trong qu trnh cng hng, cc bc chuyn gia hai mc nng lng lin k, t

mc thp ln mc cao (hp th) v t cao xung thp (pht x) c cng xc sut. Nh c
s khc nhau nh v s chim ch trong mc nng lng thp hn m ta quan st c s
hp th trong th nghim cng hng.
S chim ch ca mt mc nng lng ca mt nhm ht nhn trong cn bng

nhit c biu hin qua phng trnh phn b Boltzmann :


N '' E / kT
e
= e hH z / kT k = hng s Boltzmann.
N'
Trong nhng t trng thng c s dng trong NMR th s khc nhau v phn

b l cc nh. V d trong t trng Hz = 14 kG, i vi proton th

N ''
= 1,000009 c
N

ngha l c 1 triu proton (106) th ch c 10 proton nhiu hn mc nng lng thp.


S chnh lch ny gip ta ghi c ph NMR (hp th).
*) Qu trnh hi phc
Trong qu trnh cng hng, ht nhn thu nng lng (hp th) t trng xoay

chiu m ta chiu vo. Do s chnh lch v s chim ch gia hai mc nng lng l qu
nh nn s nhanh chng b cn bng v tn hiu hp th s bin mt ("bo ho").
Mt khc, ht nhn cng cho mt nng lng trong khi cng hng thng qua trao

i nng lng vi mi trng xung quanh hoc gia cc ht nhn vi nhau mt cch

52

khng pht x. Qu trnh ny gi l qu trnh hi phc. Qu trnh hi phc c tc dng


chng li s "bo ho" trong khi cng hng.
Qua qu trnh hi phc th trng thi cn bng trong mu c thit lp gia "bo

ho" v "phn b Boltzmann".


Qu trnh hi phc bo m cho vic lun lun o c tn hiu cng hng, mc

d chiu vo mu mt t trng cao tn.


Mi loi ht nhn c mt tc hi phc c trng.
S hi phc chm trong mu s to ra trng thi gn s bo ho v tn hiu hp th

nh. S hi phc rt nhanh s lm kh quan st tn hiu hp th, v nng lng thu t t


trng xoay chiu cao tn b trao i ngay vi mi trng m khng to ra bc nhy.
Qu trnh hi phc c nh hng n thi gian sng ca cc trng thi nng lng

v do nh hng n rng ca tn hiu hp th.


Tnh cht ca mu nh hng rt ln n tc hi phc. Vi cc mu nht cao

hoc mu rn th tc hi phc nhanh do tn hiu rt rng.


Tng t, nu trong mu c nhng ht l lng hoc cc cht thun t (cht c in

t t do) th vch cng rng.


T trng Hz cng tc ng vo tc hi phc. Hz khng ng nht (inhomogen)

vch rng phn gii km.


3. Phn t v t trng hiu dng (Molecules and effective field)
Qu trnh hp th nng lng t t trng cao tn xoay chiu ca cc ht nhn ca
mt ng v c cng gi tr khng phi ch c quyt nh bi cng t trng Ho
m cn bi cc t trng ph, nh ca mi trng phn t xung quanh ht nhn. Ta c :
Hz = HO + HDD + HA + HSS
Hz : cng t trng hiu dng ti ht nhn
HO : cng t trng ca thit b
HDD : cng t trng xut hin do tng tc dipol dipol.
HA : cng t trng xut hin do s che chn in t
HSS : cng t trng xut hin do tng tc spin spin gin tip.
ln ca HDD, HA, HSS do trng thi lin kt ca cc ht nhn quyt nh. V d :

i vi 1H :
H0 = 104 G
53

HDD = 10

... 101 G
1

HA = 0 ... 10

HSS = 0 ... 10

Nhng ht nhn ca mt ng v c lin kt khc nhau s hp th mc nng

lng h khng i ti cc trng HO khc nhau.


cht rn HDD s c nh hng ln nht, do c qu trnh hi phc nhanh, nn cc

vch rt rng.
II. C s thc nghim
C hai kh nng xc nh s hp th cng hng : Hoc gi t trng HO c

nh v thay i tn s ca t trng xoay chiu cao tn hoc gi tn s t trng xoay


chiu c nh v thay i H0 cho n khi c cng hng.
Mu nm gia hai u ca mt cc nam chm in. T trng c to thnh bi

dng in mt chiu n nh.


T trng xoay chiu cao tn c to thnh bi mt my pht cao tn v tc ng

vo mu thng qua mt cun dy.


ghi c ph th H0 phi thay i (sweep). Vic ny do my sweep thc hin

(sweep generator). Nng lng do mu gii phng tr li c a n b thu, c


khuch i v a vo my ghi. Ngi ta ghi cng tn hiu theo s thay i cng
t trng H0.
nhy ca cc ht nhn trong cng mt t trng.

Ho = 23487 G

1
19

nhy tng i

11

13
14

31

N
20

40

60

80

100

Tnh ng nht v s n nh ca t trng rt quan trng i vi ph NMR. V d,


1
phn gii c vch khc nhau di 1 Hz trong H NMR, my 60 MHz cn n

nh v ng nht ca t trng tt hn 10 8, c ngha l trong qu trnh o, hai i lng

54

ny khng c dao ng qu 10 6%. Vi nhng my c tn s cao hn th yu cu ny


cn cao hn.
III. Ph NMR phn gii cao
1. chuyn dch ho hc

S xung tn s radio, tip theo l thi gian thu nhn (FID) v khong cch ngt gia
hai xung (pulse delay)

Cu to s lc ca mt my cng hng t ht nhn

55

T trng ph HA c gy ra bi nhng in t xung quanh ht nhn.


Qua H0 xut hin dng in vng ca lp v in

t quanh ht nhn xut hin HA. HA t l thun vi H0


nhng ngc chiu H0 :
HA = H0
: hng s che chn
V in t che chn ht nhn trc t trng H0. Ti
ht nhn ta c : (nu b qua HSS)
HZ = H0 H0 = H0(1 )
t c cng cng hng HR th cng t trng ca thit b phi tng

ln mt gi tr H0. Gi tr ny bng gi tr che chn t ca ht nhn.


Nhng tn hiu ca cc ht nhn b che chn ging nhau s trng nhau. Nhng ht

nhn ny c gi l tng ng v ho hc (chemically equivalent).


Khong cch gia hai tn hiu ca proton A v B b che chn khc nhau trong ph

NMR l:
HR = HR(B) HR(A) = H0(B A)
Khong cch ny ngoi s ph thuc vo hng s che chn A, B cn ph thuc vo
t trng ca thit b H0.
H R
Ngc li : B A =
=
H0

khng ph thuc vo t trng ca thit b. c gi l chuyn dch ho hc.


A(mu) =

H R
H R(chun)

H R(chun) H R(mu)
H R(chun)

Khi tn s l c nh.
V HR c gi tr rt nh nn chuyn dch ho hc c t cho n v l ppm
6

(part per million); 1 ppm = 10 .

chuyn dch ho hc l i lng c trng cho nhng ht nhn b che chn

tng ng ca mt hp cht. N c tnh bng ppm v khng ph thuc vo t trng


ca thit b H0.

56

Cht chun phi l nhng cht c nhng ht nhn b che chn nh nhau, tc l ch

cho mt tn hiu trong ph NMR. Cho 1H-NMR thng l TMS; ngi ta t cho TMS
= 0 ppm.
*) nh hng ca mt in t n : Vng ca i vi cc loi proton rt rng.
C ngha l v tr cng hng ca mt nhn proton nht nh s thay i theo loi v cu
trc trong phn cn li ca phn t. Nguyn nhn l s thay i mt in t ca proton
ta ang quan st bi tnh m in ca nguyn t bn cnh hoc nhm bn cnh.
V d : + Cc metyl halogenid:
Hp cht

Tnh m in ca halogen

chuyn dch ho hc
(ppm)

CH3J

3,0

2,15

CH3Br

3,2

2,65

CH3Cl

3,5

3,01

CH3F

4,0

4,22

+ OH, NH: tham gia to lin kt hiro che chn thay i, bin ng ln, ph
thuc vo loi lin kt, bn lin kt, nng , dung mi, nhit ...
V d : Trong MeOH tinh khit lin kt H mnh OH = 5,05, trong 1 M CH3OH
trong CCl4 OH = 3,7 ppm.
*) nh hng ca s bt ng hng (anisotropy) : Hiu ng che chn ln nht l t
cc nhm chc c in t .
V d nhn thm : T trng H0 gy ra t trng ngc chiu HA trong phn nhm,
c ng sc t trng ngc vi t trng H0. Vng ngoi vng thm th HA v H0 l
cng chiu. Nh vy l s che chn do nhn thm gy ra xung quanh n l bt ng
hng (anisotrop). Hiu qu l cc ht nhn nhng vng khc nhau c tn hiu b lch
khc nhau. Proton vng () s dch v trng H0 thp, proton vng (+) s dch v
trng H0 cao.
+ Do hiu ng anisotropy ca lin kt CC m : Ha hoc Ra b che chn mnh hn He
hoc Re.

57

Khong chuyn dch ho hc ca mt s n v cu trc quan trng

chuyn dch ho hc ca proton nhm OH, SH, NH (, ppm, CCl4 hoc CDCl3).

58

*) nh hng bi s bt ng hng : vng benzen vi dng in vng, >C=O,


>C=C<, >CC<

Khng c
dng in vng

C dng
in vng

Thnh phn t trng


i vi proton nhn
thm ngoi vng

M hnh dng in vng


benzen

Hnh nn d hng
ca benzen

*) nh hng bi mt in t
CH

CH2

H
CH

12

CH

OH

11

10

H
H

H
CH3

H
H

H
H

H
H

CH3
H

H
H

(H ngoi) : -0,51
(vng) : 7,27; 6,95

(vng) : 8,14; 8,64


(CH 3 ) = - 4,25

(H ngoi) : 9,28
(trong) : -2,99

59

Biu din hiu ng d hng ca lin kt C = C, C = O v NO2

Hnh nn d hng ca lin kt n C - C v lin kt - C C -

H (e) - H (a) 0,5ppm

a
e

e
e

CH3

(e)

- CH3

(a)

0,1 - 0,2 ppm

e
a

*) chuyn dch ho hc lin quan n cu trc v cho thng tin v cu trc


Tt c cc chuyn dch pha trng thp hn s c gi tr dng ( skala).

Ngoi ra cn thc ( skala) vi TMS = 10 ppm.


S che chn cng ln th tn hiu cng dch v bn phi ca ph v ngc li.
Ht nhn hoc cc nhm ht nhn tng tc vi nhau c gi l h spin (spin

system)
Trong ph NMR mi hng s tng tc phi c xc nh hai tn hiu, nu

tng tc xy ra gia cc ht nhn ca cng mt ng v.

60

Dung mi trong cng hng t ht nhn.


Dung mi
Tetraclorometan (CCl4)
Cacbon sunfua (CS2)
Hexaclo-1,3-butadien (C4Cl6)
Diclodiflorometan (CCl2F2)
[D1] Cloroform (CDCl3)
[D4] Metanol (CD3OD)
[D6] Axeton (CD3COCD3)
[D6] Benzen (C6D6)
[D12] Cyclohexan (C6D12)
[D8] Toluen (C6D5CD3)
[D5] Nitrobenzen (C6D5NO2)

[D2] Diclorometan (CD2Cl2)


[D1] Bromoform (CDBr3)
[D2] 1,1,2,2,-Tetracloroetan (C2D2Cl4)
[D3] Axetonitril (CD3CN)
[D10] Dietyl ete (C4D10O)
[D8] Tetrahidrofuran (C4D8O)
[D8] Dioxan (C4D8O2)
[D6] Dimetyl sunfoxit (CD3SOCD3)
[D5] Pyridin (C5D5N)

[D2] Nc (D2O)
[D4] Axit axetic (CD3COOD)
[D1] Axit trifloroaxetic (F3CCOOD)
[D18] Axit hexametyl photpho triamit
(HMPT) [(CD3)2N)]3PO

Hp th ()
7,24
3,35
4,78
2,04
7,27
1,42
2,30
7,19
7,50
7,67
8,11
5,32
6,83
6,00
1,93
1,07
1,73
3,58
3,58
2,49
7,19
7,55
8,71
4,65
2,03
11,5
2,53

*
T

So vi hp cht khng tero ha


C th dng o nhit thp

C th o nhit cao

nc (oC)
23
112 T
21
160 T
64,
98 T

T.si (oC)
77
46
215 H
- 30
61
64

95 T
6
7
95

56
80
81
111

211 H

97T
8
44
45
116T
108 T

40
150 H
146 H
82
35
66

12
19
42

102
189H
115

0
17
15

100
118
72

233H

61

Ph 1H-NMR ca cloroform trong axeton-d6


vi cc tn hiu nhiu : D3C CO CHD2, H2O
R : vch ph do quay ng mu qu lu (vch gi)
SC : vch v tinh

13

C (tng tc

13

C H trong CHCl3)

SSi : vch v tinh 29Si (tng tc 29Si 1H trong TMS)


*) Ph bc cao
1

Trong ph H NMR thng cc tn hiu ca cc ht nhn tng tc rt gn nhau.

iu kin ph bc 1 s khng c thc hin, ta c ph bc cao. gii thch ph bc


cao thi nhng quy tc n gin v bi, t l cng s khng cn ng na. Xut
hin hiu ng mi nh.
H spin :

Dng ph
V d : a) CH3CHO

A3X hoc AX3

b) CH3 O CH 2 CH 2 O CH3

A3H2 hoc A2H3

c) CH3 CH 2 S CH3

A4 (c 4 proton nhm CH2 l tng


ng v t

HA

HB

Cl

NO 2
HA'

HB'

AA'BB' (2 proton A v 2 proton B c cng


chuyn dch ho hc nhng khng tng
ng v t. Chng tng tc vi o-proton
mnh hn vi p-proton : J H A HB > J H A HB'

62

c iu kin cho ph bc 1 th ngoi iu kin

AX
> 6 cn cn iu kin
J AX

tng ng v t ca tt c cc ht nhn tng tc vi nhau.


*) bi (s vch) ca mt tn hiu c tnh :
S vch = 2NI + 1
I = s lng t spin ht nhn
N = s ht nhn tng ng v t bn cnh.
Cng thc ny ch ng cho ph bc 1, tc l hiu ca chuyn dch ho hc ca
ht nhn tng tc ln hn hng s tng tc.
i j

> 6 hay
>6
I ij
J

Cho nhng ht nhn c I =

1
s vch = N + 1
2
H

H'
F

H''

H'

H''

H'''
1H

19F

Dng vch xut hin do tng tc spin ht nhn trong ph bc 1


S ht nhn tng tc
nm cnh vi spin:
I = 1/2

I=1

S vch
( bi)

Cng tng i

1 (Singulet)

2 (Dublet)

1:1

3 (Triplet)

1:2:1

4 (Quartet)

1:3:3:1

5 (Quintet)

1:4:6:4:1

6 (Sextet)

1 : 5 : 10 : 10 : 5 : 1

7 (Septet)

1 : 6 : 15 : 20 : 15 : 6 : 1

1 (Singulet)

3 (Triplet)

1:1:1

5 (Quintet)

1:2:3:2:1

7 (Septet)

1:3:6:7:6:3:1

63

2. Tng tc spin spin gin tip


2.1. C ch tng tc
Cc t trng ph ca cc ht nhn bn cnh tng tc vi ht nhn ta nghin cu

thng qua cc in t trong lin kt ho hc, bi vy l tng tc gin tip.


Tng tc spin spin xy ra gia cc ht nhn cng loi (homonuclear) v khc

loi (heteronuclear). Tc l trng thi spin ca ht nhn A tc ng vo t trng ti ht


nhn X m n tng tc v ngc li.
V d : 1, 1, 2 - tricloetan
Cl

Cl

Cl

H"

H'
TMS

J
TMS

H' v H'' c cng mi trng ho hc cng chuyn dch ho hc. Nguyn t


1
1
H c hai trng thi + v (song song v ngc vi H0). Nh vy n gy ra hai t
2
2
trng ph H' v H''. Liu t trng ph do H gy ra cho H' khi t trng ca H song
song vi t trng H0 lm mnh hay yu t trng ca H' l ty thuc vo cc lin kt
gia H v H' v c biu th bng du + hay du ca J. V c nhiu H song song v
ngc chiu H0 nn H' c hai vch ta gi l dublet. Khong cch gia hai vch l hng
s tng tc J gia H v H'. Tn hiu ca H'' cng tch thnh dublet, nhng chng kht ln
dublet ca H'.
H' v H'' cng gy ra t trng ph vi H.

H'

1 : 2 : 1 (cng )

H''
T trng ph = 0 c xc sut gp hai.
Nh vy tn hiu ca H tch thnh 3 vch (triplet), trong vch gia c cng
gp i .
2.2. Tnh cht ca hng s tng tc J :
J khng ph thuc vo t trng ca thit b (H0)
64

Khng quan st thy J nu cc ht nhn tng tc c cng , ngi ta c th tnh


c J ny.
J cng nh nu tng tc cng qua nhiu lin kt.
J ph thuc vo lin kt v cu trc phn t.
2.3. Tng tc geminal : (2J)
L tng tc gia nhng proton qua hai lin kt
H
H
C
Jgem 0 20 Hz, ngoi l : J = 43 Hz
2.4. Tng tc vicinal
H
L tng tc qua ba lin kt H
J
0 20 H v dng. C C
vicinal

2.4.1. Tng tc vicinal qua hai nguyn t C sp3 (2J).


*) ln ca s tch vch do tng tc
Hng s tng tc trong ph bc 1 l khong cch gia hai vch lin nhau xut hin
do tng tc.
th Karplus (xem phn sau)
*) bi ca cc tn hiu
M = 2nI + 1
1
1
1
1
19 1
3
Nu cc ht nhn I = tng tc vi nhau (v d H/ H, H/ F, H/ P...) th
2
M=n+1
Nu hiu s ca chuyn dch ho hc ca cc tn hiu ca cc ht nhn tng tc
vi nhau (v d AX = |A x|) ln hn nhiu so vi hng s tng tc: AX

J AX

> 6 th ta

c ph bc 1.
Trong ph NMR thng cc tn hiu b tch thnh nhiu vch, nguyn nhn l do
tng tc spin spin gia cc ht nhn.
2.4.1.1. Ph thuc vo gc nh din :

th Karplus
S ph thuc ny c Karplus chng minh bng l thuyt v khng nh qua
kinh nghim thc tin.

65

3. Cng tn hiu
Trong ph NMR cng tn hiu c xc nh bi s khc nhau v chim ch
mc nng lng gy ra bi phn b Boltzmann :
S ~ (N'' N')
ng tch phn

4. Hiu ng NOE. Ph NOESY


5. Ph cng hng t ht nhn 13C (13C-NMR)

Ph 13C-NMR ca axit N-Axetyl--D-neuramin metyl ester (5) (D2O)

66

A: Ph 50,3 MHz- 13C-NMR ca dn xut axit neuramin (1) kh tng tc vi 1H


B: Ph 50,3 MHz- 13C-NMR APT

Ph DEPT 45, DEPT 135 v DEPT 90

67

Ph DEPT 135 ca dn xut ca axit neuramin (1)

Bng gn cc tn hiu 13C ca dn xut 1 da vo ph DEPT

Gn tn hiu

68

6. Ph hai chiu (2D)


6.1. Ph 1H11H-COSY

Ph 500-MHz-COSY-90 ca axit Glutamin (2)


Bin bn tri v pha trn l ph 500-MHz -1H-NMR gn cc tn hiu. Cc
ng vch s ni cc pic ng cho vi cc pic tng tc v cho thy cc proton
no tng tc vi nhau.
Pic ng cho ca 2 proton C-3 ni vi hai pic tng tc v hai proton ny
tng tc vi c hai proton v tr C-2 v C-4.

69

Ph 400 MHz -COSY-45 ca dn xut ca axit neuramin (1)

70

6.2. Ph HMQC
6.3. Ph HMBC

Ph tng tc H, C hai chiu 100,6 MHz ca dn xut ca axit neuramin (1)


Bin bn tri l ph 1H
Bin pha trn l ph 13C-.

71

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